CN107747222A - A kind of fluorescence organic frame based on electrostatic spinning technique and preparation method thereof - Google Patents
A kind of fluorescence organic frame based on electrostatic spinning technique and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fluorescence organic frame composite membrane based on electrostatic spinning technique and preparation method thereof.This method comprises the following steps：(1) electrospinning substrate nano fibrous membrane, (2) configuration activating solution, (3) activated base nano fibrous membrane, the growth of the MOFs crystal of (4) fluorescence property.For the preparation method of the present invention without high pressure, high temperature action in preparation process, preparation condition is gentle, can effectively reduce production cost and potential safety hazard, and the arrangement of obtained fluorescence organic frame is orderly, and yield is high, is adapted to large-scale production, has good application prospect.
Description
Technical field
The invention belongs to the preparation method field of metal organic frame and the composite of micro nanometer fiber, and in particular to
A kind of fluorescence organic frame based on electrostatic spinning technique and preparation method thereof.
Background technology
Metal-organic frame (Metal-Organic Frameworks, MOFs) refer to organic ligand and metal ion it
Between the crystalline material of multidimensional structure that is formed.It is mainly characterized by：(1) extra specific surface area；(2) by metal ion and having
The diversity of machine part allows the random regulation and control that there is MOFs superpower designability to realize aperture size and crystal structure.
Therefore, in past 20 years, MOFs gas separation, gas absorption, gas storage, magnetic, ultracapacitor, water process,
There is potential application in the fields such as medicament slow release, catalysis, chemical sensor and fluorescence detection.Due to the sensing based on fluorescent quenching
Performance, therefore the MOFs crystalline materials of fluorescence are rich in because it can quickly detect explosive, VOC etc..With high sensitivity,
Reaction speed is fast, process is simple etc..Therefore there is potential application in environment measuring, Homeland Security etc..It is but most of glimmering
Light MOFs exists in the form of crystal powder shape, limits its application.
And nano fibrous membrane causes the broad interest of people due to its bigger specific surface area and big porosity,
But growth in situ MOFs composites were paid close attention to since 2010 by everybody on polymer surfaces.These composite substrate films have
Excellent physical property, it can further widen the potential scope of application of MOFs crystal.And electrostatic spinning technique be at present can be with
One of technology of continuous micro nanometer fiber film is prepared, its micro nanometer fiber film prepared there can be advantages below (1) in diameter
On, electrospinning fibre is thinner than traditional fibre, specific surface area increase；(2) higher porosity；(3) electro spinning nano fiber is easily by work(
Energyization.But the MOFs particle major part growth conditions at present by the use of electrospun fiber membrane as substrate grown photoluminescent property is more severe
Carve, be generally required for high pressure-temperature etc..For example, Chinese patent (CN102671553A) reports and utilizes electrospinning system
It is then harsher using Hydrothermal Growth MOFs, growth conditions, it is desirable to autoclave etc. for crystal seed film.
The content of the invention
The technical problem to be solved in the present invention is：Overcome prior art defect, there is provided a kind of based on electrostatic spinning technique
Fluorescence organic frame and preparation method thereof.The preparation method of the present invention, without high pressure, high temperature action, prepares bar in preparation process
Part is gentle, can effectively reduce production cost and potential safety hazard, and the arrangement of obtained fluorescence organic frame is orderly, and yield is high, is adapted to
Large-scale production, has good application prospect.
In order to solve the above problems, the invention provides a kind of preparation of the fluorescence organic frame based on electrostatic spinning technique
Method, comprise the following steps：
(1) electrospinning substrate nano fibrous membrane：Prepare the spinning containing chitosan (Chitosan) and polyethylene glycol oxide (PEO)
Precursor liquid, it is that substrate is received that chitosan/polyoxyethylene (Chitosan/PEO) nano fibrous membrane, which is made, using method of electrostatic spinning
Rice tunica fibrosa；
(2) activating solution is configured：1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine is added in phosphate buffer solution
Hydrochloride and trimesic acid are well mixed, and the pH value of solution is treated 1- ethyls-(3- dimethylaminos third to 3.8-6.4
Base) phosphinylidyne diimmonium salt hydrochlorate fully activates trimesic acid and obtains the activating solution of enough carboxyls (- COOH)；
(3) activated base nano fibrous membrane：It is obtained that substrate nano fibrous membrane obtained by step (1) is immersed into step (2)
In activating solution, abundant activated base nano fibrous membrane, carboxyl (- COOH) is linked on substrate nano fibrous membrane, sample is washed
It is standby afterwards；
(4) growth of the MOFs crystal of fluorescence property：Hydration fluorescence metal nitrate and trimesic acid are dissolved in ethanol
With solution is configured in water, fiber membrane sample made from step (3) is dipped in solution, solution is placed in closed container, to
Triethylamine is injected in container and allows it to volatilize naturally, fluorescent metal ion starts in rich carboxylic fibre with trimesic acid part
Surface-assembled is tieed up, MOFs crystal/chitosan complex film of uniform fluorescence property is grown into, produces based on electrostatic spinning technique
Fluorescence organic frame.
Pattern has been made uniformly and chitosan/polyoxyethylene rich in amino by method of electrostatic spinning first in this method
(Chitosan/PEO) then substrate nano fibrous membrane is dipped in rich carboxylic by nano fibrous membrane as substrate nano fibrous membrane
In activating solution, the carboxyl of trimesic acid in the amino linkage activating solution of substrate nano fibrous membrane, rich carboxylic fiber is obtained
Membrane sample, laid the first stone to obtain conjugation and the preferable metal organic frame of uniformity, finally, be hydrated fluorescence metal nitric acid
Salt and trimesic acid are dissolved in second alcohol and water and are configured to solution, and the fiber membrane sample that will be enriched in carboxyl is dipped in solution, will
Solution is placed in closed container, and triethylamine is injected into container and allows it to volatilize naturally, fluorescent metal ion and trimesic acid
Part starts in the rich carboxylic carboxylic fiber surface assembling of richness, to grow into MOFs crystal/shell of uniform fluorescence property
Glycan composite membrane, produce the fluorescence organic frame based on electrostatic spinning technique.The injection speed of control triethylamine in step (4)
The product of different-shape and fluorescence property can be obtained.The preparation method, without high pressure, high temperature action, can have in preparation process
Effect reduces production cost and potential safety hazard, and the arrangement of obtained fluorescence organic frame is orderly, and yield is high, is adapted to large-scale production,
With good application prospect.
Further, described step (1) electrospinning substrate nano fibrous membrane：By 0.18g polyethylene glycol oxides (PEO, molecular weight
400w) it is dissolved in 1.62g chitosans (Chitosan, molecular weight 90w) in 26.5mL 70% acetum, adjusting parameter is entered
Row electrostatic spinning：Control receives distance 10cm, voltage 15kV, and chitosan/polyoxyethylene (Chitosan/PEO) nanometer is made
Tunica fibrosa is substrate nano fibrous membrane.
Further, described step (2) configuration activating solution：300mg 1- second is added in 40mL phosphate buffer solutions
Base-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC.HCL) and 0.2g trimesic acid are well mixed, and are made molten
The pH value of liquid makes 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC.HCL) activation equal to 4.8-5.2
Benzenetricarboxylic acid 1h, obtains activating solution.
Further, described step (3) activated base nano fibrous membrane：By the substrate nanofiber obtained by step (1)
Film is immersed in activating solution made from step (2), after immersion activation 1h, takes out fiber membrane sample, standby after sample is washed.
Further, the growth of the MOFs crystal of described (4) fluorescence property：0.45g (1mmol) gadolinium nitrate hexahydrate is molten
In second alcohol and water, (volume ratio of ethanol and water is 1 to solution:1) 15mL solution As are obtained in solution, 0.42g (2mmol) trimesic acid is molten
In second alcohol and water, (volume ratio of ethanol and water is 2 to solution:1) 6mL solution Bs are obtained in solution, take 5mL solution As and the equal benzene three of 2mL respectively
Formic acid solution B is well mixed to obtain reaction solution, and fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in close
Close in container, triethylamine is injected into container and allows it to volatilize naturally, injection speed 1-10mL/h, is volatilized time 1-10min, three
After ethamine diffuses to reaction solution, gadolinium (Gd) ion starts to assemble in rich carboxylic fiber surface with trimesic acid part, raw
Grow up to MOFs crystal/chitosan complex film of uniform fluorescence property, produce the fluorescence organic frame based on electrostatic spinning technique.
Further, the growth of the MOFs crystal of described (4) fluorescence property：The nitric hydrate europiums of 0.446g (1mmol) six
Being dissolved in second alcohol and water, (volume ratio of ethanol and water is 1:1) 15mL solution As, 0.42g (2mmol) trimesic acid are obtained in solution
Being dissolved in second alcohol and water, (volume ratio of ethanol and water is 2:1) 6mL solution Bs are obtained in solution, take 5mL solution As and the equal benzene of 2mL respectively
Tricarboxylic acid solution B is well mixed to obtain reaction solution, and fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in
In closed container, triethylamine being injected into container and allows it to volatilize naturally, injection speed 1-10mL/h, volatilize time 1-10min,
After triethylamine diffuses to reaction solution, europium (Eu) ion starts to assemble in rich carboxylic fiber surface with trimesic acid part,
MOFs crystal/chitosan complex film of uniform fluorescence property is grown into, producing the fluorescence based on electrostatic spinning technique has machine frame
Frame.
Further, the MOFs crystal of the fluorescence property described in step (4) is Eu-BTC, appointing in Gd-BTC, Tb-BTC
It is a kind of.
The invention also discloses the fluorescence organic frame based on electrostatic spinning technique as made from method of the present invention.
Metal organic frame arrangement obtained by this method is orderly, prepared electrospinning micro nanometer fiber and fluorescence organic framework
Conjugation is high, has preferable mechanical property and physical property, and is easily recycled, and has preferable fluorescence property, obtained tool
There are the MOFs materials of nano-scale, make to be more widely applied, such as the biology aspect such as nuclear-magnetism radiography, drug delivery.
The beneficial effects of the invention are as follows：The invention provides a kind of fluorescence organic frame based on electrostatic spinning technique and its
Preparation method.For the preparation method of the present invention without high pressure, high temperature action in preparation process, preparation condition is gentle, can effectively drop
Low production cost and potential safety hazard, and the arrangement of obtained fluorescence organic frame is orderly, yield is high, is adapted to large-scale production, has
Good application prospect.
Brief description of the drawings
Fig. 1：The SEM of substrate nano fibrous membrane made from embodiment 1 is characterized；
Fig. 2：The SEM of fluorescence organic frame sample made from embodiment 1 is characterized；
Fig. 3：The fluorescence excitation spectrum and absorption spectra of fluorescence organic frame sample made from embodiment 1；
Fig. 4：The fluorescence excitation spectrum and absorption spectra of fluorescence organic frame sample made from embodiment 2.
Embodiment
For the technical characterstic for illustrating this programme can be understood, this programme is illustrated below by embodiment.
Embodiment 1
A kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique, comprises the following steps：
(1) electrospinning substrate nano fibrous membrane：By 0.18g polyethylene glycol oxides (PEO, molecular weight 400w) and 1.62g chitosans
(Chitosan, molecular weight 90w) is dissolved in 26.5mL 70% acetum, and adjusting parameter carries out electrostatic spinning：Control receives
Distance 10cm, voltage 15kV, it is substrate Nanowire that chitosan/polyoxyethylene (Chitosan/PEO) nano fibrous membrane, which is made,
Tie up film (gained fiber morphology is as shown in Figure 1)；
(2) activating solution is configured：300mg 1- ethyls-(3- dimethylaminos third are added in 40mL phosphate buffer solutions
Base) phosphinylidyne diimmonium salt hydrochlorate (EDC.HCL) and 0.2g trimesic acid is well mixed, make the pH value of solution to 4.8-5.2,
Allow 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC.HCL) to activate trimesic acid 1h, must activate
Liquid；
(3) activated base nano fibrous membrane：It is obtained that substrate nano fibrous membrane obtained by step (1) is immersed into step (2)
In activating solution, after immersion activation 1h, fiber membrane sample is taken out, it is standby after sample is washed；
(4) growth of the MOFs crystal of fluorescence property：0.45g (1mmol) gadolinium nitrate hexahydrate is dissolved in second alcohol and water (second
The volume ratio of alcohol and water is 1:1) 15mL solution As are obtained in solution, 0.42g (2mmol) trimesic acid is dissolved in second alcohol and water (second
The volume ratio of alcohol and water is 2:1) 6mL solution Bs are obtained in solution, take 5mL solution As and 2mL trimesic acids solution B to mix respectively
It is even to obtain reaction solution, fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in closed container, to container
Middle injection triethylamine simultaneously allows it to volatilize naturally, injection speed 1-10mL/h, and volatilize time 2min, and triethylamine diffuses to reaction solution
Afterwards, gadolinium (Gd) ion starts to assemble in rich carboxylic fiber surface with trimesic acid part, grows into uniform fluorescence
MOFs crystal/chitosan complex film of energy, producing the fluorescence organic frame based on electrostatic spinning technique, (gained fiber morphology is as schemed
Shown in 2).
There is preferable fluorescence as the fluorescence organic frame based on electrostatic spinning technique obtained by the method for embodiment 1
Can, the fluorescence excitation spectrum and absorption spectra of the sample of gained are as shown in Figure 3.
Embodiment 2
A kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique, comprises the following steps：
(1) electrospinning substrate nano fibrous membrane：By 0.18g polyethylene glycol oxides (PEO, molecular weight 400w) and 1.62g chitosans
(Chitosan, molecular weight 90w) is dissolved in 26.5mL 70% acetum, and adjusting parameter carries out electrostatic spinning：Control receives
Distance 10cm, voltage 15kV, it is substrate Nanowire that chitosan/polyoxyethylene (Chitosan/PEO) nano fibrous membrane, which is made,
Tie up film；
(2) activating solution is configured：300mg 1- ethyls-(3- dimethylaminos third are added in 40mL phosphate buffer solutions
Base) phosphinylidyne diimmonium salt hydrochlorate and 0.2g trimesic acid is well mixed, and makes the pH value of solution to 4.8-5.2, allow 1- ethyls-
(3- dimethylaminopropyls) phosphinylidyne diimmonium salt acid salt activating trimesic acid 1h, obtains activating solution；
(3) activated base nano fibrous membrane：It is obtained that substrate nano fibrous membrane obtained by step (1) is immersed into step (2)
In activating solution, after immersion activation 1h, fiber membrane sample is taken out, it is standby after sample is washed；
(4) growth of the MOFs crystal of fluorescence property：The nitric hydrate europiums of 0.446g (1mmol) six are dissolved in second alcohol and water
(volume ratio of ethanol and water is 1:1) 15mL solution As are obtained in solution, 0.42g (2mmol) trimesic acid is dissolved in second alcohol and water
(volume ratio of ethanol and water is 2:1) 6mL solution Bs are obtained in solution, take 5mL solution As and 2mL trimesic acid solution Bs to mix respectively
Uniform reaction solution is closed, fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in closed container, to
Triethylamine is injected in container and allows it to volatilize naturally, injection speed 1-10mL/h, volatilize time 2min, and triethylamine diffuses to reaction
After liquid, europium (Eu) ion starts to assemble in rich carboxylic fiber surface with trimesic acid part, grows into uniform fluorescence
MOFs crystal/chitosan complex film of performance, produces the fluorescence organic frame based on electrostatic spinning technique.
There is preferable fluorescence as the fluorescence organic frame based on electrostatic spinning technique obtained by the method for embodiment 2
Can, the fluorescence excitation spectrum and absorption spectra of the sample of gained are as shown in Figure 4.
Illustrative embodiments listed above are only not to technical scheme described in the invention for understanding that the present invention is used
Restriction, the those of ordinary skill about field, on the basis of technical scheme described in claim, a variety of changes can also be made
Change or deformation, all equivalent changes or deformation should all be covered within the claims of the present invention.The present invention is not
Part is described in detail, is the known technology of those skilled in the art of the present technique.
Claims (8)
1. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique, it is characterised in that comprise the following steps：
(1) electrospinning substrate nano fibrous membrane：The spinning precursor liquid containing chitosan and polyethylene glycol oxide is prepared, utilizes electrostatic spinning
It is substrate nano fibrous membrane that legal system, which obtains chitosan/polyoxyethylene nano fibrous membrane,；
(2) activating solution is configured：1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid is added in phosphate buffer solution
Salt and trimesic acid are well mixed, and the pH value of solution is treated 1- ethyls-(3- dimethylaminopropyls) carbon to 3.8-6.4
Acyl diimmonium salt hydrochlorate fully activates trimesic acid and obtains activating solution；
(3) activated base nano fibrous membrane：Substrate nano fibrous membrane obtained by step (1) is immersed into the obtained activation of step (2)
In liquid, abundant activated base nano fibrous membrane, carboxyl is linked on substrate nano fibrous membrane, it is standby after sample is washed；
(4) growth of the MOFs crystal of fluorescence property：Hydration fluorescence metal nitrate and trimesic acid are dissolved in second alcohol and water
In be configured to solution, fiber membrane sample made from step (3) is dipped in solution, solution is placed in closed container, to container
Middle injection triethylamine simultaneously allows it to volatilize naturally, and fluorescent metal ion starts in rich carboxylic fiber table with trimesic acid part
Face assembles, and grows into MOFs crystal/chitosan complex film of uniform fluorescence property, produces the fluorescence based on electrostatic spinning technique
Organic frame.
2. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In described step (1) electrospinning substrate nano fibrous membrane：0.18g polyethylene glycol oxides and 1.62g chitosans are dissolved in 26.5mL
In 70% acetum, adjusting parameter carries out electrostatic spinning：Control receives distance 10cm, voltage 15KV, obtained chitosan/poly-
Ethylene oxide nano fibrous membrane, as substrate nano fibrous membrane.
3. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In described step (2) configuration activating solution：300mg 1- ethyls-(3- dimethylaminos are added in 40mL phosphate buffer solutions
Base propyl group) phosphinylidyne diimmonium salt hydrochlorate and 0.2g trimesic acid is well mixed, and makes the pH value of solution to 4.8-5.2, allow 1-
Ethyl-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt acid salt activating trimesic acid 1h, obtains activating solution.
4. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In described step (3) activated base nano fibrous membrane：Substrate nano fibrous membrane obtained by step (1) is immersed into step (2) system
In the activating solution obtained, after immersion activation 1h, fiber membrane sample is taken out, it is standby after sample is washed.
5. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In the growth of the MOFs crystal of described (4) fluorescence property：0.45g gadolinium nitrate hexahydrates are dissolved in ethanol and the aqueous solution and obtained
15mL solution As, the volume ratio of ethanol and water described in solvent is 1:1,0.42g trimesic acid is dissolved in ethanol and the aqueous solution
In 6mL solution Bs, the volume ratio of ethanol and water described in solvent are 2:1,5mL solution As and 2mL trimesic acids are taken respectively
Solution B is well mixed to obtain reaction solution, and fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in into closed appearance
In device, triethylamine is injected into container and allows it to volatilize naturally, injection speed 1-10mL/h, volatilize time 1-10min, triethylamine
After diffusing to reaction solution, gadolinium ion starts to assemble in rich carboxylic fiber surface with trimesic acid part, grows into uniformly
Fluorescence property MOFs crystal/chitosan complex film, produce the fluorescence organic frame based on electrostatic spinning technique.
6. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In the growth of the MOFs crystal of described (4) fluorescence property：The nitric hydrate europiums of 0.446g six are dissolved in ethanol and the aqueous solution and obtained
15mL solution As, the volume ratio of ethanol and water described in solvent is 1:1,0.42g trimesic acid is dissolved in ethanol and the aqueous solution
In 6mL solution Bs, the volume ratio of ethanol and water described in solvent are 1:1,5mL solution As and 2mL trimesic acids are taken respectively
Solution B is well mixed to obtain reaction solution, and fiber membrane sample made from step (3) is dipped in reaction solution, solution is placed in into closed appearance
In device, triethylamine is injected into container and allows it to volatilize naturally, injection speed 1-10mL/h, volatilize time 1-10min, triethylamine
After diffusing to reaction solution, europium ion starts to assemble in rich carboxylic fiber surface with trimesic acid part, grows into uniformly
Fluorescence property MOFs crystal/chitosan complex film, produce the fluorescence organic frame based on electrostatic spinning technique.
7. a kind of preparation method of the fluorescence organic frame based on electrostatic spinning technique as claimed in claim 1, its feature exist
In the MOFs crystal of the fluorescence property described in step (4) is Eu-BTC, any of Gd-BTC, Tb-BTC.
8. as the fluorescence organic frame based on electrostatic spinning technique obtained by any method in claim 1 to 7.
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| CN108816064A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material |
| CN109433120A (en) * | 2018-10-30 | 2019-03-08 | 武汉纺织大学 | Have pollutant absorption, catalysis and nanofiber gel material of fluorescence tracking synergistic function and preparation method thereof |
| CN112726027A (en) * | 2020-12-28 | 2021-04-30 | 青岛大学 | Film with detection effect on divalent copper ions in waste liquid and preparation and application thereof |
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| IRAJ KOHSARI等: "Antibacterial electrospun chitosan-polyethylene oxide nanocomposite mats containing ZIF-8 nanoparticles", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
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| CN108444500A (en) * | 2018-03-12 | 2018-08-24 | 天津大学 | Flexible sensing device based on metal-organic framework material and preparation method thereof |
| CN108816064A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material |
| CN109433120A (en) * | 2018-10-30 | 2019-03-08 | 武汉纺织大学 | Have pollutant absorption, catalysis and nanofiber gel material of fluorescence tracking synergistic function and preparation method thereof |
| CN109433120B (en) * | 2018-10-30 | 2021-02-26 | 武汉纺织大学 | Nanofiber gel material with pollutant adsorption, catalysis and fluorescence tracking synergistic functions and preparation method thereof |
| CN112726027A (en) * | 2020-12-28 | 2021-04-30 | 青岛大学 | Film with detection effect on divalent copper ions in waste liquid and preparation and application thereof |
| CN112726027B (en) * | 2020-12-28 | 2022-06-07 | 青岛大学 | Film with detection effect on divalent copper ions in waste liquid and preparation and application thereof |
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